DE10324101A1 - Fuel compositions with improved cold flow properties - Google Patents

Abstract

The invention relates to the use of copolymers which contain at least one acrylate ester polymerized derived from a heteroatom-functionalized alcohol, as an additive for fuel oils and lubricating oils and in particular as a cold flow improver in fuel oils; the fuel oils and lubricant oils additized with these copolymers and additive packages containing such copolymers.

Description

The The invention relates to the use of copolymers which are at least an acrylic ester polymerized from a heteroatom-functionalized Alcohol derives as an additive for fuel oils and lubricants and especially as cold flow improvers in fuel oils; the fuel oils and lubricants additized with these copolymers; such as Additive packages containing such copolymers.

State of the art:

paraffinic Waxes containing mineral oils, such as middle distillates, diesel and heating oils, show at temperature lowering a significant deterioration of the flow properties. The cause therefor lies in the crystallization occurring from the temperature of the cloud point of longer Paraffins, the big, platy wax crystals form. These wax crystals have a sponge-like structure and lead to include other fuel constituents in the crystal composite. The appearance of these crystals leads quickly for bonding fuel filters both in tanks and in tanks Motor vehicles. At temperatures below the pour point (PP) finally finds no flow of fuel anymore.

to Solving these problems has been fuel additives for a long time added in small concentrations, often from combinations of Nucleators to the early Formation of small crystallites of paraffins with the actual cold flow improvers (also known as CFI or MDFI). These in turn show similar Crystallization properties such as the paraffins of the fuel, however, prevent their growth, allowing the filter to pass significantly lower compared to the unadditized fuel Temperatures possible is. As a measure of this is the Cold Filter Plugging Point (CFPP). As another Additive can so-called wax anti-settling additives (WASA) are used, prevent the decrease of the microcrystallites in the fuel.

cold flow improvers depending on the nature of the base fuel and the additive in amounts of about 50 to 500 ppm added. They are out of state various CFI products are known in the art (see for example US-A-3,038,479, 3,627,838 and 3,961,961, EP-A-0,261,957 or DE-A-31 41 507 and 25 15 805). Common CFI are usually polymeric compounds, in particular ethylene-vinyl acetate (EVA) copolymers, e.g. the under the trade name Keroflux sold by BASF AG products.

Also Combinations of conventional CFI with lubricity improvers (Esters of mono- or polycarboxylic acids with mono- or polyalcohols) be as improved CFI combinations described (EP-A-0 721 492).

The EP-A 0 997 517 describes a mixture of a copolymer which consists of Ethylene, another olefinically unsaturated monomer, the hydroxy groups contains and optionally further ethylenically unsaturated monomers is, and a polar nitrogenous compound. Such mixtures intended as lubricity improvers be suitable.

It is an ongoing one Need for further additives with CFI properties, in particular those which are cheaper be used, for example because they are in lesser Dosage as commercial CFI's cold flow properties of fuels or lubricants.

Short description of Invention:

It is therefore an object of the present invention, such new additives provide.

Surprisingly could solve this task Be surprised by the unexpected observation that copolymers are special Containing heteroatom-functionalized acrylic esters in copolymerized form, as CFI additives are useful and also a better performance as conventional Own EVA CFI's.

One The first object of the invention relates to the use of a copolymer, the at least one acrylic ester contains polymerized, which is functionalized by a heteroatom Alcohol derives as an additive for fuel oils and lubricants. In particular, such copolymers are used the the acrylic acid ester in copolymerized form in a statistical distribution.

Acrylic acid esters derived from a heteroatom-functionalized alcohol are understood in the context of the present application to mean compounds which are a single carbon-carbon double contain bond to which a carboxyl group COOR is directly attached, wherein the radical R is derived from a heteroatom-functionalized alcohol.

The remaining three substituents on the carbon-carbon double bond are selected from H and C ₁ -C ₄ alkyl.

Preferably is in the radical R of these acrylic acid esters at least one heteroatom bonded to a carbon atom, the α-, β-, γ- and / or δ-constantly zur Carboxyl group of the acrylic ester stands. In particular, the heteroatom is bonded to a carbon atom, that β-constant to Carboxyl group of the acrylic acid ester is.

The Heteroatom can be over a single, double or triple bond to the one carrying it Be bound carbon atom. Preferably it is over one Bound single bond.

Under Heteroatoms are all understood in the context of the present invention different from carbon and hydrogen elements with Carbon one under usual Ambient conditions (room temperature, humidity, light radiation etc.) and polymerization conditions undergo stable covalent bonding and the use according to the invention of the copolymer does not conflict. These include e.g. Si, O, S, N and P.

Preferably if the heteroatom is oxygen.

worin
R¹ für H oder C₁-C₄₀-, wie z.B. C₁-C₂₀-, insbesondere C₁-C₁₀-, vorzugsweise C₁-C₄-Hydrocarbyl steht;
R², R³, R⁴ und R⁵ gleich oder verschieden sind und für H, C₁-C₄₀-, wie z.B. C₁-C₂₀-, insbesondere C₁-C₁₀-, vorzugsweise C₁-C₄-Hydrocarbyl, -COOR¹⁴ oder -OCOR¹⁴ stehen, wobei R¹⁴ für C₁-C₄₀-, wie z.B. C₁-C₂₀-, insbesondere C₁-C₁₀-, vorzugsweise C₁-C₄-Hydrocarbyl steht und wobei wenigstens einer der Reste R², R³, R⁴ und R⁵ für -COOR¹⁴ oder -OCOR¹⁴ steht;
R⁶, R⁷ und R⁸ gleich oder verschieden sind und für H oder C₁-C₄-Alkyl stehen und
R⁹ für COOR¹⁰ steht,
wobei R¹⁰ für eine Gruppe der Formel -[-A-O-]-_nR¹¹ steht, worin A für C₂-C₄-Alkylen steht,
R¹¹ für H, C₁-C₁₀-Alkyl oder für einen 3- bis 16-gliedrigen carbo- oder heterocyclischen, gesättigten, ein- oder mehrfach ungesättigten Ring oder für ein entsprechendes kondensiertes Ringsystem steht und
n für eine Zahl von 1 bis 20 steht.Preference is given to using copolymers which are essentially composed of monomers comprising the monomers M1, M2 and optionally M3, where M1, M2 and M3 have the following general formulas

wherein
R ^{1 is} H or C ₁ -C ₄₀ -, such as C ₁ -C ₂₀ -, especially C ₁ -C ₁₀ -, preferably C ₁ -C ₄ -hydrocarbyl;
R ² , R ³ , R ⁴ and R ^{5 are} identical or different and are H, C ₁ -C ₄₀ -, such as C ₁ -C ₂₀ -, in particular C ₁ -C ₁₀ -, preferably C ₁ -C ₄ - Hydrocarbyl, -COOR ¹⁴ or -OCOR ¹⁴ , wherein R ^{14 is} C ₁ -C ₄₀ -, such as C ₁ -C ₂₀ -, in particular C ₁ -C ₁₀ -, preferably C ₁ -C ₄ -hydrocarbyl and wherein at least one of R ² , R ³ , R ⁴ and R ^{5 is} -COOR ¹⁴ or -OCOR ¹⁴ ;
R ⁶ , R ⁷ and R ^{8 are the} same or different and are H or C ₁ -C ₄ alkyl and
R ^{9 stands} for COOR ¹⁰ ,
where R ^{10 is} a group of the formula - [- AO -] - _n R ¹¹ where A is C ₂ -C ₄ -alkylene,
R ^{11 is} H, C ₁ -C ₁₀ -alkyl or a 3- to 16-membered carbo- or heterocyclic, saturated, mono- or polyunsaturated ring or a corresponding condensed ring system and
n is a number from 1 to 20.

Preferably, R ^{1 is} H.

Preferably, those radicals R ² , R ³ , R ⁴ and R ⁵ , which are not COOR ¹⁴ or OCOR ^14, are H or methyl, especially H.

Preferably, R ⁶ , R ⁷ and R ^{8 are} independently H or methyl. More preferably R ⁶ and R ^{7 are} H and R ⁸ is H or methyl and especially H.

In the definition of R ¹¹ is the 3 to 6-membered, carbo- or heterocyclic, saturated or mono- to polyunsaturated ring or the corresponding fused ring system, for example, cyclopropyl, cyclopentyl, cyclohexyl, cyclooctyl, cyclodecyl, cyclopentenyl, cyclohexenyl, cyclooctenyl, Cyclodecenyl, cyclopentadienyl, cyclohexadienyl, cyclooctadienyl, phenyl, cyclooctatetraenyl, oxiranyl, aziridinyl, oxolanyl, dioxolanyl, oxolenyl, dioxolenyl, furanyl, oxazolanyl, oxathiolanyl, pyrrolidinyl, pyrrolinyl, pyrrolyl, pyrazolyl, imidazolyl, oxazolyl, isoxazolyl, thiazolyl, isothiazolyl, triazolyl, Tetrazolyl, thiolanyl, dihydrothiophenyl, thiophenyl, piperidinyl, piperazinyl, morpholinyl, pyridinyl, pyridazinyl, pyrimidinyl, pyrazinyl, triazinyl, tetrahydropyranyl, pyranyl, thiopyranyl, thiazinyl, naphthyl, anthracenyl, phenanthrenyl, indolyl, carbazolyl, dibenzofuranyl, quinolinyl, isoquinolinyl, acridinyl, Phenazinyl, phenoxazinyl and the like. The rings can also be monosubstituted to polysubstituted. Suitable substituents are, for example, C ₁ -C ₄ -alkyl, C ₁ -C ₄ -alkoxy, C ₁ -C ₄ -hydroxyalkyl and hydroxyl groups.

When R ^{11 is} H, in M1 R ^{1 is} preferably H and / or the proportion x of M ³ in the copolymer is preferably 0 <x ≦ 20 mol%.

Preferably, R ^{11 is} not H.

In particular, R ^{11 is} C ₁ -C ₄ -alkyl or phenyl.

A is preferably for Ethylene.

n is preferably for a number from 1 to 10, more preferably from 1 to 5 and especially for 1 or Second

In the copolymers used according to the invention, the monomers M1, M2 and M3 may be present in the copolymer in the following molar proportions (Mx / (M1 + M2 + M3):
M1: 0.55 to 0.999, preferably 0.6 to 0.95, especially 0.7 to 0.95;
M2: 0.001 to 0.25, preferably 0.006 to 0.25, especially 0.008 to 0.22;
M3: 0 to 0.2, preferably 0 to 0.15, in particular 0.01 to 0.15.

Prefers are the inventively used Copolymers available by, preferably free-radical, polymerization, in particular high-pressure polymerization, the monomers M1, M2, and optionally M3, and in particular the Monomers M1, M2 and M3.

preferred Monomers M1 are selected under ethylene, propylene and 1-butene.

Preferred monomers M2 are selected from monomers of the following formula:

Preferred monomers M3 are selected from C ₁ -C ₂₀ -carboxylic acid vinyl esters and C ₁ -C ₂₀ -hydrocarbyl (meth) acrylates and in particular from C ₁ -C ₂₀ -carboxylic acid vinyl esters. A particularly preferred monomer M3 is vinyl acetate.

If M2 for one of the acrylic esters 1, 2 or 3 and especially for 2, M1 is preferably ethylene and / or the moiety x of M3 in the copolymer preferably 0 <x ≤ 20 mol%.

Especially preferred copolymers are selected from ethylene / acrylic acid 2- (2-ethoxyethoxy) -2-ethyl ester 2 copolymers and ethylene / acrylic acid 2- (2-ethoxyethoxy) -2-ethyl ester 2 / vinyl acetate copolymers.

Preferably the copolymers are used as cold flow improvers.

The The above-described copolymers are used alone or in combination used with other such copolymers in amounts to a Effect as cold flow improver to show in the additive fuel or lubricant.

object The present invention is also as defined above Copolymer.

One The invention further relates to fuel oil compositions, containing a larger proportion by weight one boiling in the range of about 120-500 ° C Middle distillate fuel and a minor amount by weight at least a cold flow improver according to the above Definition.

such Fuel oil compositions can as fuel component biodiesel (from animal and / or vegetable production) in proportions of 0-30% by weight.

preferred Fuel oil compositions are selected among diesel fuels, kerosene and fuel oil, the diesel fuel may be obtainable by refining, coal gasification or gas liquefaction, a mixture represent such products and optionally with regenerative Fuels can be mixed. Such fuel oil compositions are preferred, the sulfur content of the mixture being at most 500 ppm.

One The invention further relates to lubricant compositions, containing a larger proportion by weight a conventional one Lubricant and a smaller Ge weight share at least one cold flow improver according to the above Definition.

in the Within the scope of the present invention, the copolymers according to the invention can be used in combination with other conventional ones cold flow improvers and / or further lubricating and Fuel oil additives be used.

One The last object of the invention also relates to additive packages comprising a copolymer according to the invention according to the above Definition in combination with at least one other conventional lubricating and fuel oil additive.

Detailed description the invention:

a) Copolymers of the invention

The Copolymers of the invention are preferably substantially of the monomers defined above M1, M2 and possibly M3 constructed. Depending on the manufacturing process may be necessary small proportions of one used as a regulator (chain terminator) Be included.

Unless otherwise specified, the following general definitions apply:
C ₁ -C ₄₀ -hydrocarbyl is in particular C ₁ -C ₄₀ -alkyl, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, pentyl, hexyl, heptyl, octyl , 2-ethylhexyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl, hencosyl, docosyl, tricosyl, tetracosyl, pentacosyl, hexacosyl, heptacosyl, octacosyl, nonacosyl, squalyl, and the higher homologs and the associated positional isomers. The same applies to C ₁ -C ₂₀ -hydrocarbyl radicals. C ₁ -C ₁₀ -hydrocarbyl is in particular C ₁ -C ₁₀ -alkyl, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, pentyl, hexyl, heptyl, octyl , 2-ethylhexyl, nonyl and decyl. C ₁ -C ₄ -hydrocarbyl is in particular C ₁ -C ₄ -alkyl, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl and tert-butyl.

C ₁ -C ₄ -Hydroxyalkyl is C ₁ -C ₄ -alkyl substituted by at least one hydroxy group, such as 2-hydroxyethyl, 2- and 3-hydroxypropyl, 2-, 3- and 4-hydroxybutyl.

C ₁ -C ₄ -alkoxy in particular represents methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy and tert-butoxy.

alkylene stands in particular for Methylene, ethylene, 1,2- or 1,3-propylene, 1,2-, 1,3-, 2,3-, 2,4-, 3,4- or 1,4-butylene and especially for Ethylene.

When examples for suitable monomers M1 are: mono-alkenes with non-terminal or preferably terminal double bond, in particular ethylene, Propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene and 1-decene, as well as the higher ones unsaturated Homologs with up to 40 carbon atoms.

When examples for preferred acrylic acid esters M2 may be mentioned: 2-methoxyethyl acrylate, 2-ethoxyethyl acrylate, Acrylic acid-2-propoxyethylester, Acrylic acid-2-isopropoxyethylester, Acrylic acid-2-butoxyethyl, Acrylic acid-2-isobutoxyethylester, Acrylic acid 2-tert-butoxyethyl, Acrylic acid-3-methoxypropyl, Acrylic acid-3-ethoxypropylester, Acrylic acid-3-propoxypropylester, Acrylic acid-3-isopropoxypropylester, Acrylic acid-3-butoxypropylester, Acrylic acid-3-isobutoxypropylester, Acrylic acid 3-tert-butoxypropylester, Acrylic acid-2-phenoxyethyl, Acrylic acid-3-phenoxypropylester, Acrylic acid-2-benzyloxyethylester, Acrylic acid-3-benzyloxypropylester, acrylate of diethylene glycol monomethyl, ethyl and propyl ether, acrylic ester of triethylene glycol monomethyl, ethyl and propyl ether, acrylic ester of tetraethylene glycol monomethyl, ethyl and propyl ethers and acrylic esters of pentaethylene glycol monomethyl, ethyl or propyl ether. One particularly preferred acrylic acid esters is the acrylic acid ester of diethylene glycol monoethyl ether 2 (2- (2-ethoxyethoxy) ethyl acrylate; Aeee).

Examples of suitable monomers M3 are:
C ₁ -C ₂₀ -carboxylic acid vinyl esters, in particular the vinyl esters of formic acid, acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, enanthic acid, caprylic acid, pelargonic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, arachic acid, behenic acid, lignoceric acid, cerotic acid and melissic acid; furthermore C ₁ -C ₂₀ -alkyl acrylates and C ₁ -C ₂₀ -alkyl methacrylates, in which C ₁ -C ₂₀ -alkyl is methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, Pentyl, hexyl, heptyl, octyl, 2-ethylhexyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl or eicosyl.

The copolymers of the invention also have a number average molecular weight M _n in the range of about 1000 to 20,000, particularly preferably from 1000 to 10,000 and in particular from 1000 to 6000.

The copolymers may also have a weight-average molecular weight M _{w of} from 1000 to 30 000, in particular from 1500 to 15 000 and / or an M _w / M _n ratio of from 1.5 to 5.0, in particular from 1.8 to 4.0.

Particularly preferred copolymers are composed of the monomers ethylene, acrylic ester 2 (acrylic acid 2- (2-ethoxyethoxy) ethyl ester, AEEE) and optionally vinyl acetate (VAC). Based on the polymer, the proportion by weight of the monomers is:
VAC: 0-42 wt.%, Preferably 0 to 35 wt.%, Especially about 1 to 30 wt.%, Especially 1 to 20 wt.%
AEEE: 2-70% by weight, preferably 2.5 to 70% by weight, in particular about 3.5 to 65% by weight

The viscosity of such copolymers (determined according to Ubbelohde DIN 51562) is about 5 -25,000 mm ² / s, in particular about 10 to 1000 mm ² / s, each at a temperature of about 120 ° C.

b) Preparation of the copolymers

The Copolymers of the invention are prepared by methods known per se, preferably according to the prior art (see, e.g., Ullmann's Encyclopedia of Industrial Chemistry 5th edition, keyword: Waxes, Vol. A 28, p. 146 ff., Weinheim VCH, Basel, Cambridge, New York, Tokyo, 1996) known methods for direct radical high pressure copolymerization unsaturated Links.

The Preparation of the copolymers is preferably carried out in stirred high pressure autoclave or in high pressure tube reactors or combinations of both. at behave them predominantly The relationship Length / diameter in ranges of 5: 1 to 30: 1, preferably 10: 1 to 20: 1.

suitable Printing conditions for the polymerization is 1000 to 3000 bar, preferably 1500 to 2000 bar. The reaction temperatures are e.g. in the range of 160 to 320 ° C, preferred in the range of 200 to 280 ° C.

oder Mischungen derselben.As a regulator for adjusting the molecular weight of the copolymers used, for example, an aliphatic aldehyde or an aliphatic ketone of the general formula I.

or mixtures thereof.

• – Wasserstoff;
• – C₁-C₆-Alkyl, wie Methyl, Ethyl, n-Propyl, iso-Propyl, n-Butyl, iso-Butyl, sec.-Butyl, tert.-Butyl, n-Pentyl, iso-Pentyl, sec-Pentyl, neo-Pentyl, 1,2-Dimethylpropyl, iso-Amyl, n-Hexyl, iso-Hexyl, sec-Hexyl; besonders bevorzugt C₁-C₄-Alkyl, wie Methyl, Ethyl, n-Propyl, iso-Propyl, n-Butyl, iso-Butyl, sec-Butyl und tert.-Butyl;
• – C₃-C₁₂-Cycloalkyl, wie Cyclopropyl, Cyclobutyl, Cyclopentyl, Cyclohexyl, Cycloheptyl, Cyclooctyl, Cyclononyl, Cyclodecyl, Cycloundecyl und Cyclododecyl; bevorzugt sind Cyclopentyl, Cyclohexyl und Cycloheptyl;

The radicals R ^a and R ^{b are the} same or different and selected from

• - hydrogen;
• C ₁ -C ₆ -alkyl, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, sec-butyl Pentyl, neo-pentyl, 1,2-dimethylpropyl, iso-amyl, n-hexyl, iso-hexyl, sec-hexyl; particularly preferably C ₁ -C ₄ -alkyl, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl and tert-butyl;
• C ₃ -C ₁₂ cycloalkyl, such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, cycloundecyl and cyclododecyl; preferred are cyclopentyl, cyclohexyl and cycloheptyl;

The radicals R ^a and R ^b may also be covalently linked together to form a 4- to 13-membered ring. For example, R ^a and R ^b may together form the following alkylene groups: - (CH ₂ ) ₄ -, - (CH ₂ ) ₅ -, - (CH ₂ ) ₆ , - (CH ₂ ) ₇ -, -CH (CH ₃ ) -CH ₂ -CH ₂ -CH (CH ₃ ) - or -CH (CH ₃ ) -CH ₂ -CH ₂ -CH ₂ -CH (CH ₃ ) -.

The Use of propionaldehyde or ethyl methyl ketone as regulator very particularly preferred.

Further well-suited regulators are unbranched aliphatic hydrocarbons, such as propane or branched aliphatic hydrocarbons with tertiary H atoms, such as isobutane, isopentane, isooctane or Isododecane (2,2,4,6,6-pentamethylheptane). As another additional Regulators can use higher olefins, such as propylene used.

Also Mixtures of the above regulators with hydrogen or hydrogen alone are also preferred.

The Amount of regulator used is the usual for the high-pressure polymerization Amounts.

• – Didecanoylperoxid, 2,5-Dimethyl-2,5-di(2-ethylhexanoylperoxy)hexan, tert-Amylperoxy-2-ethylhexanoat, Dibenzoylperoxid, tert-Butylperoxy-2-ethylhexanoat, tert-Butylperoxydiethylacetat, tert-ßutylperoxydiethylisobutyrat, 1,4-Di(tert-butylperoxycarbo)-cyclohexan als Isomerengemisch, tert-Butylperisononanoat, 1,1-Di-(tert-butylperoxy)-3,3,5-trimethylcyclohexan, 1,1-Di-(tert-butylperoxy)-cyclohexan, Methyl-isobutylketonperoxid, tert-Butylperoxyisopropylcarbonat, 2,2-Di-tert-butylperoxy)butan oder tert-Butylperoxacetat;
• – tert-Butylperoxybenzoat, Di-tert-amylperoxid, Dicumylperoxid, die isomeren Di-(tert-butylperoxyisopropyl)benzole, 2,5-Dimethyl-2,5-di-tert-butylperoxyhexan, tert-Butylcumylperoxid, 2,5-Dimethyl-2,5-di(tert-butylperoxy)-hex-3-in, Di-tert-butylperoxid, 1,3-Diisopropylmonohydroperoxid, Cumolhydroperoxid oder tert-Butylhydroperoxid; oder
• – dimere oder trimere Ketonperoxide, so wie sie z.B. aus der EP-A-0 813 550 bekannt sind

As starters for the radical polymerization, the usual radical initiators, such as organic peroxides, oxygen or azo compounds, can be used. Also mixtures of several radical starters are suitable. As free-radical initiators, it is possible, for example, to use one or more peroxides selected from the following commercially available substances:

• - Didecanoyl peroxide, 2,5-dimethyl-2,5-di (2-ethylhexanoylperoxy) hexane, tert-amylperoxy-2-ethylhexanoate, dibenzoyl peroxide, tert-butyl peroxy-2-ethylhexanoate, tert-butyl peroxydiethylacetate, tert-butylperoxydiethylisobutyrate, 1,4 -Di (tert-butylperoxycarbo) -cyclohexane as a mixture of isomers, tert-butyl perisononanoate, 1,1-di (tert-butylperoxy) -3,3,5-trimethylcyclohexane, 1,1-di- (tert-butylperoxy) -cyclohexane, Methyl isobutyl ketone peroxide, tert-butyl peroxy isopropyl carbonate, 2,2-di-tert-butylperoxy) butane or tert-butyl peroxyacetate;
• Tert-butyl peroxybenzoate, di-tert-amyl peroxide, dicumyl peroxide, the isomeric di (tert-butylperoxyisopropyl) benzenes, 2,5-dimethyl-2,5-di-tert-butylperoxyhexane, tert-butylcumyl peroxide, 2,5-dimethyl 2,5-di (tert-butylperoxy) -hex-3-yne, di-tert-butyl peroxide, 1,3-diisopropyl monohydroperoxide, cumene hydroperoxide or tert-butyl hydroperoxide; or
• Dimeric or trimeric ketone peroxides, as are known, for example, from EP-A-0 813 550

When Peroxides are di-tert-butyl peroxide, tert-butyl peroxypivalate, tert-butyl peroxyisononanoate or dibenzoyl peroxide or mixtures thereof are particularly suitable. As azo compound is azobisisobutyronitrile ("AIBN") called by way of example. The radical starters are used in polymerizations Doses are metered.

In a preferred procedure, the copolymers of the invention are prepared by reacting a mixture of the monomers M1, M2 and optionally M3 in the presence of the regulator at a temperature in the range of about 20 to 50 ° C, such as 30 ° C, preferably continuously a Rührautokla which is maintained at a pressure in the range of about 1500 to 2000 bar, such as about 1700 bar. By the preferably continuous addition of initiator, which is usually dissolved in a suitable solvent, such as isododecane, the temperature in the reactor at the desired reaction temperature, such as at 200 to 250 ° C, held. The resulting after the relaxation of the reaction mixture polymer is then isolated in a conventional manner.

modifications This driving style is natural possible and can be made by the skilled person without undue burden. So, for example the comonomers and the regulator are added separately to the reaction mixture The reaction temperature can be varied during the process are just a few examples.

c) fuel oil compositions

Under Fuel oil compositions is understood according to the invention preferably Fuels. Suitable fuels are gasolines and middle distillates, like diesel fuels, heating oil or kerosene, with diesel fuel and heating oil being particularly preferred.

at the fuel oils For example, these are low-sulfur or high-sulfur Petroleum raffinates or around stone or lignite distillates, which usually have a boiling range from 150 to 400 ° C exhibit. Preferably, the fuel oils are low in sulfur heating oils, for example, those with a maximum sulfur content 0.1 wt .-%, preferably of at most 0.05% by weight, more preferably of at most 0.005% by weight, and especially from at most 0.001% by weight. As examples of heating oil was in particular heating oil for domestic oil firing systems or fuel oil Called EL. The quality requirements for such Fuel oils are specified, for example, in DIN 51-603-1 (see also Ullmann's Encyclopedia of Industrial Chemistry, 5th edition, Vol. A12, p. 617 et seq., Hereby incorporated by reference expressly Is referred).

at the diesel fuels are, for example, petroleum raffinates, the usual have a boiling range of 100 to 400 ° C. These are mostly distillates with a 95% point up to 360 ° C or even about it out. This can but also so-called "Ultra low sulfur diesel "or" City diesel "be characterized by a 95% point of, for example, a maximum of 345 ° C and a Sulfur content of not more than 0.005 wt .-% or by a 95% point for example 285 ° C and a maximum sulfur content of 0.001% by weight. In addition to the through Refining available Diesel fuels are those produced by coal gasification or gas liquefaction ("gas to liquid" (GTL) fuels) available are suitable. Also suitable are mixtures of the abovementioned Diesel fuels with renewable fuels, such as biodiesel or bioethanol.

Especially the additive according to the invention is preferred for the addition of low-sulfur diesel fuels, this means with a sulfur content of less than 0.05% by weight, preferably from less than 0.02% by weight, in particular less than 0.005% by weight. and especially less than 0.001% by weight of sulfur or for additization of heating oil with a low sulfur content, for example with a sulfur content of at the most 0.1 wt .-%, preferably of at most 0.05 wt .-%, more preferably of at most 0.005 wt .-%, and in particular from at most 0.001% by weight.

The Inventive additive is preferably in a proportion based on the total amount the fuel oil composition, used that for seen a substantially sufficient influence on the Cold flow properties of fuel oil compositions has. Most preferably, the additive is in an amount of 0.001 to 1 wt .-%, in particular from 0.01 to 0.1 wt .-%, based on the total amount of the fuel oil composition used.

d) co-additives

The Copolymers of the invention can individually or as a mixture of such copolymers and optionally in Combination with other additives known per se to the fuel oil compositions be added.

Suitable additives which may be included in the fuel oils of this invention besides the copolymer of the present invention, especially for diesel fuels and heating oils, include detergents, corrosion inhibitors, dehazers, demulsifiers, antifoams, antioxidants, metal deactivators, multifunctional stabilizers, cetane improvers, combustion improvers, dyes, Markers, solubilizers, antistatics, lubricity improvers, and other the cold properties of the Fuel-improving additives, such as nucleators, further conventional flow improvers ("MDFI"), paraffin dispersants ("WASA") and the combination of the latter two additives ("WAFI") (see also Ullmann's Encyclopedia of Industrial Chemistry, 5th Edition, Vol .A16, p.719 ff; or the patents cited for flow improvers).

• a) Copolymere von Ethylen mit wenigstens einem weiteren ethylenisch ungesättigten Monomer;
• b) Kammpolymere;
• c) Polyoxyalkylene;
• d) polare Stickstoffverbindungen;
• e) Sulfocarbonsäuren oder Sulfonsäuren oder deren Derivate; und
• f) Poly(meth)acrylsäureester.

Other conventional cold flow improvers which may be mentioned in particular are:

• a) copolymers of ethylene with at least one further ethylenically unsaturated monomer;
• b) comb polymers;
• c) polyoxyalkylenes;
• d) polar nitrogen compounds;
• e) sulfocarboxylic acids or sulfonic acids or their derivatives; and
• f) poly (meth) acrylic esters.

at the copolymers of ethylene with at least one other ethylenic unsaturated Monomer a), the monomer is preferably selected from alkenylcarboxylic esters, (Meth) Acrylsäureestern and olefins.

suitable Olefins are, for example, those having 3 to 10 carbon atoms and from 1 to 3, preferably 1 or 2, in particular one, Carbon-carbon double bond. In the latter case, the carbon-carbon double bond both terminal (α-olefins) as well as internally. However, preferred are α-olefins, especially preferably α-olefins having 3 to 6 carbon atoms, such as propene, 1-butene, 1-pentene and 1-hexene.

Suitable (meth) acrylic esters are, for example, esters of (meth) acrylic acid with C ₁ -C ₁₀ -alkanols, in particular with methanol, ethanol, propanol, isopropanol, n-butanol, sec-butanol, isobutanol, tert-butanol, pentanol, hexanol, Heptanol, octanol, 2-ethylhexanol, nonanol and decanol.

suitable alkenylcarboxylic For example, the vinyl and propenyl esters of carboxylic acids with 2 to 20 carbon atoms, whose hydrocarbon radical is linear or can be branched. Preferred among these are the vinyl esters. Under the carboxylic acids with branched hydrocarbon radical are preferred those whose Branching in the α-position to the carboxyl group wherein the α-carbon atom is especially preferably tertiary is, d. H. the carboxylic acid a so-called neocarboxylic acid is. Preferably, however, the hydrocarbon radical of the carboxylic acid is linear.

Examples for suitable alkenylcarboxylic are vinyl acetate, vinyl propionate, vinyl butyrate, vinyl 2-ethylhexanoate, neopentanoate, hexanoate, neononanoate, neodecanoate and the corresponding propenyl esters, with the vinyl esters being preferred are. A particularly preferred alkenyl carboxylic acid ester is vinyl acetate.

Especially Preferably, the ethylenically unsaturated monomer is selected under Alkenylcarboxylic esters.

Suitable are also copolymers that are two or more different from each other alkenylcarboxylic polymerized, wherein these are in the alkenyl function and / or in the carboxylic acid group. Also suitable are copolymers which, in addition to the alkenylcarboxylic ester (s) at least one olefin and / or at least one (meth) acrylic ester incorporated in copolymerized form.

The ethylenically unsaturated Monomer is in the copolymer in an amount of preferably 1 to 50 mol%, particularly preferably from 10 to 50 mol% and in particular from 5 to 20 mol .-%, based on the total copolymer, copolymerized.

The copolymer a) preferably has a number-average molecular weight M _{n of} from 1,000 to 20,000, more preferably from 1,000 to 10,000 and in particular from 1,000 to 6,000.

worin
D für R¹⁷, COOR¹⁷, OCOR¹⁷, R¹⁸, OCOR¹⁷ oder OR¹⁷ steht,
E für H, CH₃, D oder R¹⁸ steht,
G für H oder D steht,
J für H, R¹⁸, R¹⁸COOR¹⁷ Aryl oder Heterocyclyl steht,
K für H, COOR¹⁸, OCOR¹⁸, OR¹⁸ oder COOH steht,
L für H, R¹⁸COOR¹⁸, OCOR¹⁸, COOH oder Aryl steht,
wobei
R¹⁷ für einen Kohlenwasserstoffrest mit wenigstens 10 Kohlenstoffatomen, vorzugsweise mit 10 bis 30 Kohlenstoffatomen, steht,
R¹⁸ für einen Kohlenwasserstoffrest mit wenigstens einem Kohlenstoffatom, vorzugsweise mit 1 bis 30 Kohlenstoffatomen, steht,
m für einen Molenbruch im Bereich von 1,0 bis 0,4 steht und
n für einen Molenbruch im Bereich von 0 bis 0,6 steht.Comb polymers b) are, for example, those described in "Comb-Like Polymers, Structure and Properties", NA Platé and VP Shibaev, J. Poly. Sci. Macromolecular Revs. 8, pages 117 to 253 (1974) are described. Of the described there, for example, comb polymers of the formula II are suitable

wherein
D is R ¹⁷ , COOR ¹⁷ , OCOR ¹⁷ , R ¹⁸ , OCOR ¹⁷ or OR ¹⁷ ,
E is H, CH ₃ , D or R ¹⁸ ,
G is H or D,
J is H, R ¹⁸ , R ¹⁸ COOR ^{17 is} aryl or heterocyclyl,
K is H, COOR ¹⁸ , OCOR ¹⁸ , OR ¹⁸ or COOH,
L is H, R ¹⁸ COOR ¹⁸ , OCOR ¹⁸ , COOH or aryl,
in which
R ^{17 is} a hydrocarbon radical having at least 10 carbon atoms, preferably having 10 to 30 carbon atoms,
R ^{18 is} a hydrocarbon radical having at least one carbon atom, preferably having 1 to 30 carbon atoms,
m for a mole fraction in the range of 1.0 to 0.4 and
n represents a mole fraction in the range of 0 to 0.6.

preferred Comb polymers are, for example, by the copolymerization of Maleic anhydride or fumaric acid with another ethylenically unsaturated monomer, for example with an α-olefin or an unsaturated one Esters, such as vinyl acetate, and subsequent esterification of the anhydride or acid function obtainable with an alcohol of at least 10 carbon atoms. Further preferred comb polymers are copolymers of α-olefins and esterified comonomers, for example, esterified copolymers of styrene and maleic anhydride or esterified copolymers of styrene and fumaric acid. Also mixtures of comb polymers are suitable. Comb polymers can also be polyfumarates or polymaleinates. In addition, homo- and copolymers vinyl ethers suitable comb polymers.

Suitable polyoxyalkylenes c) are, for example, polyoxyalkylene esters, ethers, esters / ethers and mixtures thereof. The polyoxyalkylene compounds preferably contain at least one, particularly preferably at least two, linear alkyl groups having from 10 to 30 carbon atoms and a polyoxyalkylene group having a molecular weight of up to 5,000. The alkyl group of the polyoxyalkylene radical preferably contains from 1 to 4 carbon atoms. Such polyoxyalkylene compounds are described, for example, in EP-A-0 061 895 and in US Pat US 4,491,455 which is incorporated herein by reference in its entirety. Preferred polyoxyalkylene esters, ethers and esters / ethers have the general formula III R ¹⁹ - [- O- (CH ₂ ) _y -] - _x OR ²⁰ (III) wherein
R ¹⁹ and R ^{20 are} each independently R ²¹ , R ^{21 is} -CO-, R ^{21 is} -O-CO (CH ₂ ) _z - or R ^{21 is} -O-CO (CH ₂ ) _z -CO-, wherein R ²¹ is linear C ₁ -C ₃₀ -alkyl,
y is a number from 1 to 4,
x is a number from 2 to 200, and
z is a number from 1 to 4.

Preferred polyoxyalkylene compounds of the formula III in which both R ¹⁹ and R ^{20 are} R ²¹ are polyethylene glycols and polypropylene glycols having a number average molecular weight of 100 to 5,000. Preferred polyoxyalkylenes of the formula III in which one of the radicals R ^{19 is} R ²¹ and the other is R ²¹ -CO- are polyoxyalkylene esters of fatty acids having 10 to 30 carbon atoms, such as stearic acid or behenic acid. Preferred polyoxyalkylene compounds in which both R ¹⁹ and R ^{20 are} R ²¹ -CO- are diesters of fatty acids having 10 to 30 carbon atoms, preferably stearic or behenic acid.

The polar nitrogen compounds d), suitably oil-soluble, may be both ionic and non-ionic and preferably have at least one, more preferably at least 2, substituents of the formula> NR ²² , wherein R ^{22 is} a C ₈ -C ₄₀ hydrocarbon radical. The nitrogen substituents may also be quaternized, that is in cationic form. An example of such nitrogen ver Compounds are ammonium salts and / or amides obtainable by the reaction of at least one substituted with at least one hydrocarbon radical amine with a carboxylic acid having 1 to 4 carboxyl groups or with a suitable derivative thereof. The amines preferably contain at least one linear C ₈ -C ₄₀ -alkyl radical. Examples of suitable primary amines are octylamine, nonylamine, decylamine, undecylamine, dodecylamine, tetradecylamine and the higher linear homologs. Suitable secondary amines are, for example, dioctadecylamine and methylbehenylamine. Also suitable are amine mixtures, in particular industrially available amine mixtures, such as fatty amines or hydrogenated tallamines, as described, for example, in Ullmann's Encyclopedia of Industrial Chemistry, 6th edition, 2000 electronic release, chapter "Amines, aliphatic". Suitable acids for the reaction are, for example, cyclohexane-1,2-dicarboxylic acid, cyclohexene-1,2-dicarboxylic acid, cyclopentane-1,2-dicarboxylic acid, naphthalenedicarboxylic acid, phthalic acid, isophthalic acid, terephthalic acid and succinic acids substituted by long-chain hydrocarbon radicals.

Another example of polar nitrogen compounds are ring systems bearing at least two substituents of the formula -A-NR ²³ R ²⁴ wherein A is a linear or branched aliphatic hydrocarbon group optionally substituted by one or more groups selected from O, S , NR ³⁵ and CO, is interrupted, and R ²³ and R ^{24 are} a C ₉ -C ₄₀ -hydrocarbon radical, which is optionally interrupted by one or more groups selected from O, S, NR ³⁵ and CO, and / or substituted by one or more substituents selected from OH, SH and NR ³⁵ R ³⁶ , wherein R ^{35 is} C ₁ -C ₄₀ alkyl optionally substituted by one or more moieties selected from CO, NR ³⁵ , O and S, interrupted, and / or substituted by one or more radicals selected from NR ³⁷ R ³⁸ , OR ³⁷ , SR ³⁷ , COR ³⁷ , COOR ³⁷ , CONR ³⁷ R ³⁸ , aryl or heterocyclyl, wherein R ³⁷ and R ³⁸ each una depending on one another, are selected from H or C ₁ -C ₄ -alkyl; and R ^{36 is} H or R ³⁵ .

Preferably, A is a methylene or polymethylene group having 2 to 20 methylene units. Examples of suitable radicals R ²³ and R ²⁴ are 2-hydroxyethyl, 3-hydroxypropyl, 4-hydroxybutyl, 2-ketopropyl, ethoxyethyl and propoxypropyl. The cyclic system can be either homocyclic, heterocyclic, condensed polycyclic or non-condensed polycyclic systems. Preferably, the ring system is carbo- or heteroaromatic, in particular carboaromatic. Examples of such polycyclic ring systems are condensed benzoic structures, such as naphthalene, anthracene, phenanthrene and pyrene, condensed non-benzoidic structures, such as azulene, indene, hydrindene and fluorene, uncondensed polycycles, such as diphenyl, heterocycles, such as quinoline, indole, dihydroindole, benzofuran, Coumarin, isocoumarin, benzthiophene, carbazole, diphenylene oxide and diphenylene sulfide, non-aromatic or partially saturated ring systems such as decalin, and three-dimensional structures such as α-pinene, camphene, bornylene, norborane, norbornene, bicyclooctane and bicyclooctene.

One another example of suitable polar nitrogen compounds are long-chain primary or condensates secondary Amines with carboxyl-containing polymers.

The here mentioned polar nitrogen compounds are described in WO 00/44857 and in the references cited therein, whereupon is hereby incorporated by reference.

suitable Polar nitrogen compounds are e.g. also in DE-A-198 48 621 of DE-A-196 22 052 or EP-B-398 101, to which reference is hereby made becomes.

worin
Y für SO₃ ^–(NR²⁵ ₃R²⁶)⁺, SO₃ ^–(NHR²⁵ ₂R²⁶)⁺, SO₃ ^–(NH₂R²⁵R²⁶), SO₃ ^–(NH₃R²⁶) oder SO₂NR²⁵R²⁶ steht,
X fü_r Y, CONR²⁵R²⁷, CO₂ ^–(NR²⁵ ₃R²⁷)⁺, CO₂ ^–(NHR²⁵ ₂R²⁷)⁺, R²⁸-COOR²⁷, NR²⁵COR²⁷, R²⁸OR²⁷, R²⁸OCOR²⁷, R²⁸R²⁷, N(COR²⁵)R²⁷ oder Z^–(NR²⁵ ₃R²⁷)⁺ steht,
wobei
R²⁵ für einen Kohlenwasserstoffrest steht,
R²⁶ und R²⁷ für Alkyl, Alkoxyalkyl oder Polyalkoxyalkyl mit wenigstens 10 Kohlenstoffatomen in der Hauptkette stehen,
R²⁸ für C₂-C₅-Alkylen steht,
Z^– für ein Anionenäquivalent steht und
A und B für Alkyl, Alkenyl oder zwei substituierte Kohlenwasserstoffreste stehen oder gemeinsam mit den Kohlenstoffatomen, an die sie gebunden sind, ein aromatisches oder cyc loaliphatisches Ringsystem bilden.Suitable sulfocarboxylic acids / sulfonic acids or their derivatives e) are, for example, those of the general formula IV

wherein
Y is SO ₃ ^- (NR ²⁵ ₃ R ²⁶ ) ⁺ , SO ₃ ^- (NHR ²⁵ ₂ R ²⁶ ) ⁺ , SO ₃ ^- (NH ₂ R ²⁵ R ²⁶ ), SO ₃ ^- (NH ₃ R ²⁶ ) or SO ₂ NR ²⁵ R ²⁶ stands,
X fo _r Y, CONR ²⁵ R ^27, CO ₂ ^- (NR ²⁵ ₃ R ^{27) +,} CO ₂ ^- (NHR ²⁵ ₂ R ^{27) +} R ²⁸ COOR ^27, NR ²⁵ COR ^27, R ²⁸ OR ^27, R ^{28 is} OCOR ²⁷ , R ^{28 is} R ²⁷ , N (COR ²⁵ ) R ²⁷ or Z ^- (NR ²⁵ ₃ R ²⁷ ) ⁺ ,
in which
R ^{25 is} a hydrocarbon radical,
R ²⁶ and R ^{27 are} alkyl, alkoxyalkyl or polyalkoxyalkyl having at least 10 carbon atoms in the main chain stand,
R ^{28 is} C ₂ -C ₅ -alkylene,
Z ^{- stands} for an anion equivalent and
A and B are alkyl, alkenyl or two substituted hydrocarbon radicals or together with the carbon atoms to which they are attached form an aromatic or cycloaliphatic ring system.

such sulfocarboxylic or sulfonic acids and their derivatives are described in EP-A-0 261 957, whereupon is hereby incorporated by reference.

Suitable poly (meth) acrylic esters f) are both homo- and copolymers of acrylic and methacrylic acid esters. Preferred are copolymers of at least two mutually different (meth) acrylic acid esters, which differ with respect to the fused alcohol. Optionally, the copolymer contains a further, different of which olefinically unsaturated monomer copolymerized. The weight average molecular weight of the polymer is preferably from 50000 to 500000. A particularly preferred polymer is a copolymer of methacrylic acid and methacrylic esters of saturated C ₁₄ - ₁₅ alcohols and C, wherein the acid groups are neutralized with hydrogenated tallow amine. Suitable poly (meth) acrylic esters are described, for example, in WO 00/44857, to which reference is hereby fully made.

e) additive packages

Finally is The subject of the present application, an additive concentrate containing a copolymer of the invention as defined above and at least a diluent and optionally at least one further additive, in particular selected under the above co-additives.

Suitable diluents are, for example, fractions obtained in petroleum processing, such as kerosene, naphtha or bright stock. Also suitable are aromatic and aliphatic hydrocarbons and alkoxyalkanols. When middle distillates, especially in diesel fuels and heating oils preferred diluent used are naphtha, kerosene, diesel fuels, aromatic hydrocarbons such as Solvent Naphtha heavy, Solvesso ^® or Shellsol ^®, as well as mixtures of these solvents and diluents.

The copolymer according to the invention is in the concentrates preferably in an amount of 0.1 to 80 Wt .-%, particularly preferably from 1 to 70 wt .-% and in particular from 20 to 60% by weight, based on the total weight of the concentrate, in front.

The The invention will now be apparent from the following nonlimiting examples explained in more detail.

Experimental part:

a) Preparation Examples 1 to 16

It were a total of sixteen different copolymers of the invention by high-pressure polymerization of ethylene, acrylic ester 2 (acrylic acid 2- (2-ethoxyethoxy) -2-ethyl ester; AEEE) and optionally vinyl acetate (VAC).

ethylene, AEEE and optionally VAC were added with the addition of propionaldehyde as a regulator in a high-pressure autoclave, as in the literature Buback et al., Chem. Ing. Tech., 1994, 66, 510), polymerized.

A mixture of 12.870 kg / h of ethylene, 1.140 kg / h of vinyl acetate, 4.497 kg / h of acrylic acid ester 2 and 1.312 kg / h of propionaldehyde was passed continuously at a temperature of 30 ° C through a maintained at a pressure of 1700 bar 1 l stirred autoclave. In this case, vinyl acetate was added in the intermediate pressure range at 260 bar, the acrylic ester in the high pressure zone at 1700 bar at the preheat input and the propionaldehyde in the intermediate pressure range. By the continuous addition of 11.6 g of initiator (tert-butyl peroxypivalate, TBPP) per hour (in isododecane) in the high pressure zone at 1700 bar at the preheater outlet, the temperature in the autoclave reactor was maintained at 220 ° C. The resulting after the relaxation of the reaction mixture in an amount of 6.5 kg / h polymer corresponds to a total conversion of all starting materials of about 35%. It contains 40% by weight of ethylene, 3% by weight of vinyl acetate and 57% by weight of acrylic acid ester 2. The viscosity is 60 mm ² / s at 120 ° C.

In Table 1 are the polymerization conditions and in the table 2, the analytical data of the resulting polymers compiled.

E:

Ethylen

VAC:

Vinylacetat

AEEE:

Acrylsäureester 2

PA:

Propionaldehyd (Modifier/Regler)

TBPP:

tert-Butylperoxypivalat

ID:

Isodecan

The content of ethylene, AEEE and VAG in the obtained copolymers was determined by NMR spectroscopy. The viscosities were determined according to Ubbelohde DIN 51562. Table 1

e:

ethylene

VAC:

vinyl acetate

Aeee:

Acrylic acid ester 2

PA:

Propionaldehyde (modifier / regulator)

TBPP:

tert-butyl peroxypivalate

ID:

isododecane

Table 2

Viscosity determined according to Ubbelohde DIN 51562

b) Test Examples 1 to 3

With the above-prepared copolymers 1 to 16, the following experiments were carried out. For comparison purposes, the following conventional MDFI were tested:
MDFI A: ethylene-vinyl acetate-based polymer blend (Keroflux ES 6100, BASF AG)
MDFI B: ethylene-vinyl acetate-based polymer blend (Keroflux ES 6103, BASF AG)
MDFI C: ethylene-vinyl acetate-based polymer blend (Keroflux ES 6204, BASF AG)
MDFI D: ethylene-vinyl acetate-based polymer blend (Keroflux ES 6310, BASF AG)
MDFI E: Comparative sample: ethylene-vinyl acetate copolymer
MDFI F: Comparative sample: ethylene-vinyl acetate copolymer
MDFI G: Comparative Example: Ethylene-vinyl acetate copolymer

It became conventional Middle distillate fuels with the above invention or usual Kaltfließverbesserem Additiviert in different dosing rates and the CFPP value after DIN EN116 determined

Test Example 1

Middle distillate used: winter diesel fuel, Germany, CP = -5.9 ° C (ASTM D2500), CFPP = -9 ° C (DIN EN116), d = 825 kg / m ³ , CFPP target = -22 ° C, IBP (start of boiling) = 197 ° C., FBP (boiling end) = 358 ° C., 90-20 (temperature difference of the 90% by volume and 20% by volume of the boiling curve) = 94 ° C., 24.3% n-paraffins

The determined CFPP values (in ° C) of the additized middle distillate fuels are summarized in Table 3.

Table 3

Test Example 2

Middle distillate used: ADO, Belgium, CP = -17 ° C (ASTM D2500), CFPP = -19 ° C (DIN EN116), d = 836 kg / m ³ , CFPP target = -21 ° C, IBP = 180 ° C, FBP = 340 ° C, 90-20 = 89 ° C, 18.7% n-paraffins

The determined CFPP values (in ° C) of the additized middle distillate fuels are summarized in Table 4.

Table 4

Test Example 3

Middle distillate used: diesel fuel, Netherlands, CP = -8.6 ° C (ASTM D2500), CFPP = -9 ° C (DIN EN116), d = 838 kg / m3, CFPP target = -21 ° C, IBP = 157 ° C, FBP = 354 ° C, 90-20 = 101 ° C, 19.7% n-paraffins

The determined CFPP values (in ° C) of the additized middle distillate fuels are summarized in Table 5.

Table 5

The test results summarized in Tables 3 to 5 a surprise good performance of the copolymers of the invention as a cold flow Improver in middle distillate fuel compositions. With the inventive additives is it possible, on the one hand, comparable CFPP values as with conventional MDFIs, but at lower levels Set dosing rate, or improved at the same dosage (Higher) To achieve CFPP values.

Claims (19)

Use of a copolymer containing an acrylic ester contains polymerized, which derives from a heteroatom-functionalized alcohol, as an additive for fuel oils and lubricants. Use according to claim 1, wherein the heteroatom selected under O and N. is. Use according to one of the preceding claims, wherein the copolymer is the acrylic ester in copolymerized form in a statistical distribution. Use according to one of the preceding claims, characterized in that the copolymer is made up of the monomers comprising M1, M2 and optionally M3, where M1, M2 and M3 have the following general formulas:

wherein R ^{1 is} H or C ₁ -C ₄₀ hydrocarbyl; R ² , R ³ , R ⁴ and R ^{5 are the} same or different and are H, C ₁ -C ₄₀ -hydrocarbyl, -COOR ¹⁴ or -OCOR ¹⁴ , wherein R ^{14 is} C ₁ -C ₄₀ -hydrocarbyl and wherein at least one of R ² , R ³ , R ⁴ and R ^{5 is} -COOR ¹⁴ or -OCOR ¹⁴ ; R ⁶ , R ⁷ and R ^{8 are the} same or different and are H or C ₁ -C ₄ -alkyl and R ^{9 is} COOR ¹⁰ , wherein R ^{10 is} a group of formula - [- AO -] - _n R ¹¹ in which A is C ₂ -C ₄ -alkylene, R ^{11 is} H, C ₁ -C ₁₀ -alkyl or a 3- to 16-membered carbo- or heterocyclic, saturated, mono- or polyunsaturated ring or a corresponding condensed ring system and n is a number from 1 to 20. Use according to claim 4, characterized that the monomers M1, M2 and M3 in the following molar proportions in Copolymer are included: M1: 0.55 to 0.999 M2: 0.001 to 0.25 M3: 0 to 0.2. Use according to one of claims 4 or 5, wherein monomer M1 selected is among ethylene, propylene and 1-butene. Use according to one of the preceding claims, wherein M2 is selected from

Use according to any one of claims 4 to 7, wherein M3 is selected from C ₁ -C ₂₀ carboxylic acid vinyl esters or C ₁ -C ₂₀ hydrocarbyl (meth) acrylates. Use according to one of the preceding claims, wherein the copolymer selected is under ethylene / acrylic acid 2- (2-ethoxyethoxy) ethyl ester and ethylene / acrylic acid 2- (2-ethoxyethoxy) ethyl ester / vinyl acetate. Use according to one of the preceding claims, wherein the copolymer used as a cold flow improver becomes. Copolymer according to the definition in any one of the preceding claims. Fuel oil composition, containing a larger proportion by weight one boiling in the range of 120-500 ° C Middle distillate fuel and a minor amount by weight at least a cold flow improver according to the definition in one of the claims 1 to 11. Fuel oil composition according to claim 12, wherein the fuel component biodiesel (from animal or vegetable production) in proportions of 0-30% by weight includes. Fuel oil composition according to claim 12 selected under diesel fuels, kerosene and fuel oil. Fuel oil composition according to claim 14, wherein the diesel fuel is refined by refining, Coal gasification or gas liquefaction available is, represents a mixture of such products and optionally with regenerative Fuels is mixed. Fuel oil composition according to one of the claims 12 to 15, the sulfur content of the mixture being at most 500 ppm. Lubricant composition containing a greater proportion by weight a conventional lubricant and a smaller weight fraction of at least one cold flow improver according to the definition in one of the claims 1 to 11. Use or composition according to one of the previous ones Claims, wherein the copolymer in combination with other conventional cold flow improvers and / or other lubricating and fuel oil additives. An additive package comprising a copolymer as defined in one of the claims 1 to 10 in combination with at least one other conventional Lubricant and fuel oil additive.